U.S. patent number 4,398,020 [Application Number 06/367,618] was granted by the patent office on 1983-08-09 for production of aromatic polyketones.
This patent grant is currently assigned to Imperial Chemical Industries PLC. Invention is credited to John B. Rose.
United States Patent |
4,398,020 |
Rose |
August 9, 1983 |
Production of aromatic polyketones
Abstract
Production of an aromatic polyketone by reacting in the presence
of a fluoroalkane sulphonic acid the reactants selected from: (a) a
mixture of (i) at least one aromatic diacyl halide WOC--Ar--COW
where --Ar'-- is a divalent aromatic radical, W is halogen and COW
is an aromatically bound acyl halide group, which diacyl halide is
polymerizable with the at least one aromatic compound of (ii), and
(ii) at least one aromatic compound H--Ar'--H where --Ar'-- is a
divalent aromatic radical and H is an aromatically bound hydrogen
atom, which compound is polymerizable with the at least one diacyl
halide of (i); (b) at least one aromatic monoacyl halide
H--Ar"--COW where --Ar"-- is a divalent aromatic radical and H, W,
and COW are as defined in (a), which monoacyl halide is
self-polymerizable; and (c) a combination of (a) and (b).
Inventors: |
Rose; John B. (Letchworth,
GB2) |
Assignee: |
Imperial Chemical Industries
PLC (London, GB2)
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Family
ID: |
10521481 |
Appl.
No.: |
06/367,618 |
Filed: |
April 12, 1982 |
Foreign Application Priority Data
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Apr 29, 1981 [GB] |
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8113231 |
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Current U.S.
Class: |
528/207; 528/125;
528/126; 528/128; 528/173; 528/176; 528/179; 528/190; 528/191;
528/206; 528/220; 528/223; 528/226; 528/271; 528/360 |
Current CPC
Class: |
C08G
61/02 (20130101); C08G 61/127 (20130101); C08G
2261/124 (20130101); C08G 2261/45 (20130101); C08G
2261/3442 (20130101); C08G 2261/3444 (20130101); C08G
2261/3424 (20130101) |
Current International
Class: |
C08G
61/00 (20060101); C08G 61/02 (20060101); C08G
61/12 (20060101); C08G 067/00 () |
Field of
Search: |
;528/125,126,128,173,176,190,220,271,179,360,191,223,226,206,207 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1060546 |
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Mar 1967 |
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GB |
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1086021 |
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Oct 1967 |
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GB |
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1164817 |
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Sep 1969 |
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GB |
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1326144 |
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Aug 1973 |
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GB |
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1471171 |
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Apr 1977 |
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GB |
|
Other References
Polyarylsulfones, Synthesis and Properties, Journal of Polymer
Science, Part A-1, vol. 8, 2035-2047 (1970). H. A. Vogel..
|
Primary Examiner: Lee; Lester L.
Attorney, Agent or Firm: Cushman, Darby & Cushman
Claims
I claim:
1. A process for the production of an aromatic polyketone which
comprises reacting at a temperature of from 40.degree. to
200.degree. C. in the presence of a fluoroalkane sulphonic acid the
reactants selected from the group consisting of:
(a) a mixture of substantially equimolar amounts of
(i) at least one aromatic diacyl halide of formula
where --Ar-- is a divalent aromatic radical, W is halogen and COW
is an aromatically bound acyl halide group, which diacyl halide is
polymerisable with the at least one aromatic compound of (a)(ii),
and
(ii) at least one aromatic compound of formula
where --Ar'-- is a divalent aromatic radical and H is an
aromatically bound hydrogen atom, which compound is polymerisable
with the at least one diacyl halide of (a)(i)
(b) at least one aromatic monoacyl halide of formula
where --Ar"-- is a divalent aromatic radical and H is an
aromatically bound hydrogen atom, W is halogen, and COW is an
aromatically bound acyl halide group, which monoacyl halide is
self-polymerisable, and
(c) a combination of (a) and (b).
2. A process according to claim 1 wherein the fluoroalkane
sulphonic acid used is trifluoromethane sulphonic acid or
difluoromethane sulphonic acid.
3. A process according to claim 1 wherein the amount of
fluoroalkane sulphonic acid used is such that the fluoroalkane
sulphonic acid acts as a reaction solvent.
4. A process according to claim 1 wherein the halogen W in the
aromatic mono- or diacyl halide is Br or Cl.
5. A process according to claim 1 wherein the at least one aromatic
diacyl halide of (a) (i) is selected from the group consisting of:
##STR18## where --Y-- is a direct link, --O--, --S--, --CO--,
--SO.sub.2 --, --C(CF.sub.3).sub.2 --, or ##STR19## where n is 1 or
2, m is 1 or 2, k is 0 or 1, --X-- and --X'-- which may be the same
or different are each a direct link, --O--, --S--, --CO--,
--SO.sub.2 --, or --C(CF.sub.3).sub.2 --, and --Z-- is --CO--,
--SO.sub.2 --, or --C(CF.sub.3).sub.2 --.
6. A process according to claim 5 wherein the at least one aromatic
diacyl halide is selected from the group consisting of:
##STR20##
7. A process according to claim 1 wherein the at least one aromatic
compound of (a) (ii) is selected from the group consisting of:
##STR21## where --E-- is a direct link, --O--, --S--, or ##STR22##
where x is 1 or 2, y is 1 or 2, z is 0 or 1, --G-- and --G'-- which
may be the same or different are each a direct link, --O--, or
--S--, and --J-- is --CO--, --SO.sub.2 --, or --C(CF.sub.3).sub.2
--.
8. A process according to claim 1 wherein the at least one aromatic
monoacyl halide of (b) is selected from the group consisting of:
##STR23## where --L-- is a direct link, --O--, --S--, or ##STR24##
where p is 1 or 2, q is 1 or 2, r is 0 or 1, --R-- is a direct
link, --O--, or --S--, --R'-- is a direct link, --O--, --S--,
--CO--, --SO.sub.2 --, or --C(CF.sub.3).sub.2 --, and --Q--is
--CO--, --SO.sub.2 -- or --C(CF.sub.3).sub.2.
9. A process according to claim 8 wherein the at least one aromatic
monoacyl halide is selected from the group consisting of:
##STR25##
10. A process according to claim 8 wherein the at least one
aromatic monoacyl halide is selected from 4-phenyl benzoyl chloride
and 4-phenoxy benzoyl chloride.
Description
The present invention relates to a process for the production of
aromatic polyketones.
Aromatic polyketones are thermoplastic polymers which are well
known to the art. They are of significant commercial utility in
view of their excellent electrical insulating and mechanical
properties at high temperatures, their high strength and toughness
and their excellent resistance to fire and chemicals.
It is known, e.g. from British Pat. Nos. 1,086,021 and 1,164,817,
to produce aromatic polyketones by electrophilic aroylation
processes which utilize a reaction between a mixture of an aromatic
diacyl halide and an aromatic compound containing at least two
aromatically bound hydrogen atoms, or a self-reaction of an
aromatic monoacyl halide containing at least one aromatically bound
hydrogen atom, or a reaction involving the use of all three types
of compound, in the presence of a metallic salt, such as an Fe
salt, or a BF.sub.3 /liquid HF mixture, these materials acting as
Friedel-Crafts catalysts. Such systems do, however, have their
drawbacks: for example a BF.sub.3 /liquid HF mixture is extremely
corrosive and physiologically harmful and its use requires the
employment of pressure equipment, while the use of metallic salts
may lead to contamination problems in the resulting polymer.
I have now discovered a process for making aromatic polyketones
which, while involving the polymerisation of an aromatic mono- or
diacyl halide, does not require the use of a BF.sub.3 /liquid HF
mixture or a metallic salt as the polymerisation catalyst.
According to the present invention there is provided a process for
the production of an aromatic polyketone which comprises reacting
in the presence of a fluoroalkane sulphonic acid the reactants
selected from the following class:
(a) a mixture of
(i) at least one aromatic diacyl halide of formula
where --Ar-- is a divalent aromatic radical, W is halogen and COW
is an aromatically bound acyl halide group, which diacyl halide is
polymerisable with the at least one aromatic compound of
(a)(ii),
(ii) at least one aromatic compound of the formula
where --Ar'-- is a divalent aromatic radical and H is an
aromatically bound hydrogen atom, which compound is polymerisable
with the at least one diacyl halide of (a)(i),
(b) at least one aromatic monoacyl halide of formula
where --Ar"-- is a divalent aromatic radical and H is an
aromatically bound hydrogen atom, W is halogen, and COW is an
aromatically bound acyl halide group, which monoacyl halide is
selfpolymerisable, and
(c) a combination of (a) and (b).
Thus the process of the invention employs a fluoroalkane sulphonic
acid as the polymerisation catalyst instead of a BF.sub.3 /liquid
HF mixture or a metallic salt. While being corrosive, these
sulphonic acids are far easier and safer to handle than a liquid
HF/BF.sub.3 mixture and do not leave metallic residues. The ability
of the aromatic mono- or diacyl halides to undergo electrophilic
polymerisation in the presence of these compounds is unusual and
hitherto unsuspected. It is thought that the fluoroalkane sulphonic
acid acts as a Lewis acid in the polymerisation. The preferred
fluoroalkane sulphonic acids are trifluoromethane sulphonic acid
CF.sub.3 SO.sub.2 OH, difluoromethane sulphonic acid CF.sub.2
HSO.sub.2 OH, and tetrafluoroethane sulphonic acid CF.sub.2
HCF.sub.2 SO.sub.2 OH. Other fluoroalkane sulphonic acids which may
be used are the higher members of a series of fluoroalkane
sulphonic acids containing 1 to 18 carbon atoms (which may be fully
fluorinated as described in GB No. 758 467 or partially
fluorinated), e.g. the fluoroethane and fluoropropane sulphonic
acids such as CF.sub.3 CF.sub.2 SO.sub.2 OH and CF.sub.3 CF.sub.2
CF.sub.2 SO.sub.2 OH. It is convenient to adjust the amount of
fluoroalkane sulphonic acid used so that the acid acts as the
reaction solvent. The use of a reaction system which comprises a
more catalytic (i.e. much smaller) quantity of the fluoroalkane
sulphonic acid is not, however, excluded from the scope of the
invention.
In reaction sub-class (a), it is preferable that substantially
equimolar quantities of said at least one aromatic diacyl halide
and said at least one aromatic compound (as defined) are
employed.
Generally speaking, to effect the process of the invention, it is
convenient to dissolve or disperse the aromatic reactants in the
fluoroalkane sulphonic acid followed by a period of reaction at the
selected reaction temperature.
The halogen W in the aromatic mono- or diacyl halide is preferably
Br or Cl, and is particularly Cl.
The at least one aromatic diacyl halide of (a)(i) is preferably
selected from: ##STR1## where --Y-- is a direct link, --O--, --S--,
--CO--, --SO.sub.2 --, --C(CF.sub.3).sub.2 -- or ##STR2## where n
is 1 or 2, m is 1 or 2, k is 0 or 1, --X-- and --X'-- which may be
the same or different are each a direct link, --O--, --S--, --CO--,
--SO.sub.2 --, or --C(CF.sub.3).sub.2 --, and --Z-- is --CO--,
--SO.sub.2 --, or --C(CF.sub.3).sub.2 --.
The at least one aromatic compound of (a)(ii) is preferably
selected from: ##STR3## where --E-- is a direct link, --O--, --S--,
or ##STR4## where x is 1 or 2, y is 1 or 2, z is 0 or 1, --G-- and
--G'-- which may be the same or different are each a direct link,
--O--, or --S--, and --J-- is --CO--, --SO.sub.2 --, or
--C(CF.sub.3).sub.2 --.
The at least one aromatic monoacyl halide of (b) is preferably
selected from: ##STR5## where --L-- is a direct link, --O--, --S--,
or ##STR6## where p is 1 or 2, q is 1 or 2, r is 0 or 1, --R-- is a
direct link, --O--, or --S--, --R'-- is a direct link, --O--,
--S--, --CO--, --SO.sub.2 --, or --C(CF.sub.3).sub.2 --, and --Q--
is --CO--, --SO.sub.2 -- or C(CF.sub.3).sub.2 --.
The aromatic substances (as defined) which are used in the process
of the invention are preferably unsubstituted in the aromatic
nucleii (i.e. apart from the substituents present as indicated in
the formulae in (a) and (b)); nuclear substitution tends to affect
the activity of the aromatic substances in the polymerisation
reaction. Nevertheless, nuclear-substituted aromatic substances may
be employed in the present invention providing that the substituent
or substituents do not deleteriously affect the polymerisation
reaction or the properties of the polymer so produced. Whether or
not the position and nature of a nuclear substituent has a
deleterious effect may be discovered by experimentation.
In reactant sub-class (a)(i) of the invention, examples of aromatic
diacyl halides which may be used are: ##STR7## while examples of
aromatic compounds in (a)(ii) which may be used are: ##STR8##
In reactant class (b) of the invention, examples of aromatic
monoacyl halides which may be used are: ##STR9##
The aromatic polyketones produced by the process of the invention
may have repeating units of the general formulae:
and
according to the aromatic substances used for the
polymerisation.
The monoacyl halides 4-phenoxy benzoyl chloride and 4-phenyl
benzoyl chloride are particularly useful monomers to use in the
process of the invention since polymerisation of the former can
yield a polymer of repeat unit which is the same as that of
hitherto commercially available aromatic polyketone of consisting
substantially of the "all para" repeat unit ##STR10## while
polymerisation of the latter can yield a potentially useful polymer
of consisting substantially of the "all para" repeat unit
##STR11##
The aromatic polyketones produced by the process of the present
invention normally have a reduced viscosity (RV) of at least 0.15.
(RV in this specification unless otherwise specified is measured at
25.degree. C. on a solution of the polymer in conc. sulphuric acid
of density 1.84 g cm.sup.-3, said solution containing 1 g of
polymer per 100 cm.sup.3 of solution).
The conditions required for the polymerisation reaction (for
example, inter alia, reaction temperature and time) to produce the
aromatic polyketone should be determined by experiment as they will
vary with the nature of the starting monomer (or monomers) used and
with the desired properties of the polymer being manufactured.
Conveniently the pressure employed may be atmospheric. A normal
reaction temperature range is 40.degree. to 200.degree. C.,
particularly 50.degree. to 150.degree. C.
The invention is now illustrated by the following Examples.
EXAMPLE 1
4-Phenyl benzoyl chloride (21.65 g, 0.1 mole) was charged to a
3-necked flask (capacity 100 ml) fitted with a thermometer, stirrer
and nitrogen inlet, and condensers (leading to a nitrogen bubbler
in KOH solution so that HCl evolution could be followed by
titration). Trifluoromethane sulphonic acid (30 ml, 0.34 mole) was
introduced (under a nitrogen blanket) at the thermometer neck (at
ambient temperature--about 20.degree. C.) using a syringe. Slow
effervescence of HCl gas began immediately. The flask contents
(dark red in colour) were heated to 40.degree. C. using an oil bath
and stirred at this temperature overnight. The temperature was then
raised to 70.degree. C. over 1.5 hours and maintained at this
temperature for 5 hours. The viscous solution was poured into 1
liter of water and the resulting precipitate allowed to stand in
the water for about 48 hours. The precipitated solid was then
filtered off, ground to yield small particles (mostly less than 1
mm), washed once with 1.5 liters of boiling aqueous potassium
bicarbonate solution, thrice with 1.5 liters of boiling water and
twice with 1.5 liters of a 2/1 methanol/acetone mixture. The
product was finally dried overnight at 120.degree. C. in a vacuum
oven.
The polymer thus produced had an nmr spectrum (220 M Hz) which
showed it to be an aromatic polyketone consisting predominantly of
the repeat units having the formula ##STR12##
The yield of polymer obtained was 17.57 g (97.6% of theoretical)
and its RV was 0.86 and final melting point, Tm, 365.degree. C.
EXAMPLE 2
The equipment employed was that used in Example 1, and the
procedure was essentially the same. 4-Phenoxy benzoyl chloride
(23.25 g, 0.1 mole) was charged to the flask and trifluoromethane
sulphonic acid (20 ml) added at ambient temperature (20.degree.
C.), a further quantity (10 ml) being added after about 0.5 hours
(making 30 ml, 0.34 mole, added in total). The initial reaction was
very vigorous. A red solution was formed initially which darkened
considerably as the reaction progressed. The flask contents were
stirred at ambient temperture for about 19 hours and a sample
(Sample A) taken, poured into 600 ml water and worked up
essentially as in Example 1. A further 20 ml of trifluoromethane
sulphonic acid were added and the solution in the flask stirred for
80 hours at ambient temperature. A further sample (Sample B) was
taken and worked up as per Sample A. The solution in the flask was
stirred at 70.degree. C. overnight, at 90.degree. C. for the next
day, again at 70.degree. C. overnight, and finally at 90.degree. C.
for 2 hours the following day. The run was terminated by pouring
the solution into water whereupon a white lace precipitated; this
was soaked overnight in aqueous sodium bicarbonate solution and
then macerated. A sample (Sample C) of this was further worked up
as per Samples A and B.
The polymers of Samples A, B and C all had an nmr spectrum which
showed them to be an aromatic polyketone consisting predominantly
of the repeat units having the formula ##STR13##
The RVs of the samples were found to be as follows:
______________________________________ Sample A RV 0.41 Sample B RV
0.76 Sample C (final polymer) RV 1.02
______________________________________
EXAMPLE 3
Terephthaloyl chloride (20.3 g, 0.1 mole) was weighed into a
3-necked flask (capacity 250 ml) fitted with a stirrer, nitrogen
inlet, and condensers (leading to a nitrogen bubbler in NaOH
solution). Trifluoromethane sulphonic acid (40 ml) was added to
give a yellow/amber mixture with some of the terephthaloyl chloride
remaining undissolved. 4,4'-Diphenoxy-benzophenone (36.64 g, 0.1
mole) dissolved in 60 ml trifluoromethane sulphonic acid was added
via a dropping funnel to the stirred mixture in the flask. The
reaction started and the mixture had become very viscous after
about 40% of the addition; the temperature of the reaction mixture
was therefore slowly increased to 40.degree. C., and then to
50.degree. C. by the end of the addition. Finally the reaction
mixture was heated to 100.degree. C. and left overnight. The
resulting mixture was poured into water to yield a pale orange lace
as a precipitate. This was washed with water, twice with warm
sodium bicarbonate solution, twice with hot water and twice with
warm methanol/acetone mixture. The product was finally oven dried,
the weight of dry polymer being 48.2 g.
The polymer thus produced was an aromatic ketone consisting
predominantly (according to its nmr spectrum) of the repeat units
having the formula ##STR14## and having an RV of 0.25.
EXAMPLE 4
The equipment used was that employed in Example 3 and the procedure
essentially the same. Terephthaloyl chloride (20.3 g, 0.1 mole) was
charged to the flask and trifluoromethane sulphonic acid (40 ml)
added to give a yellow amber mixture.
4,4'-Diphenoxy-diphenylsulphone (40.24 g, 0.1 mole) dissolved in 70
ml trifluoromethane sulphonic acid were added and the reaction
contents heated after half the addition to 30.degree. C., and then
to 40.degree. C. by the end of the addition. The temperature was
increased to 50.degree. C. for 2 hours to complete the reaction,
and the reaction mixture then heated at 100.degree. C. overnight.
The mixture was poured into water to yield a buff lace as a
precipitate; the work-up of this was per Example 3, the weight of
dry polymer being 53.7 g.
The polymer produced had an nmr spectrum which showed it to be an
aroamtic polyketone consisting predominantly of the repeat units
having the formula ##STR15##
The RV of the polymer was 0.35 and it had a melting point Tm of
380.degree. C.
EXAMPLE 5
The equipment used was that employed in Example 3. Terephthaloyl
chloride (30.45 g, 0.15 mole) was weighed into the flask and 95 ml
trifluoromethane sulphonic acid added to give a pale yellow
solution. Diphenyl ether (25.53 g, 0.15 mole) was dissolved in 50
ml of trifluoromethane sulphonic acid to give a deep red solution.
This was gradually added, via a dropping funnel, to the stirred
flask contents at 22.degree. to 32.degree. C. over 2.5 hours. The
reaction mixture (a viscous solution) was then heated to
100.degree. C. over 45 minutes and left at 105.degree. C. for 19
hours. A sample of the mixture was poured into water to yield a
precipitate which was worked up as per Example 3.
The polymer produced had an nmr spectrum which showed it to be an
aromatic polyketone consisting predominantly of repeat units of
formula ##STR16## The RV of the polymer was 0.23.
EXAMPLE 6
The equipment used was that employed in Example 3. DiPhenyl (9.25
g, 0.06 mole) and 4,4'-diphenoxy-diphenylsulphone (24.15 g, 0.06
mole) were weighed into the flask and 75 ml trifluoromethane
sulphonic acid added to give a pale orange-brown solution. A
solution of terephthaloyl chloride (24.36 g, 0.12 mole) in 50 ml of
trifluoromethane sulphonic acid was carefully prepared and added
via a dropping (warming occasionally to prevent the terephthaloyl
chloride from crystallising out of solution) over 2.5 hours at
25.degree. to 35.degree. C. The reaction mixture was then heated to
100.degree. C. and kept at 105.degree. C. for 19 hours. A sample of
the mixture was worked up as per Example 3.
The polymer produced was an aromatic polyketone copolymer
consisting predominantly of repeat units of formulae ##STR17##
having an RV of 0.17.
* * * * *